月桂酸改性剂对氮化铝粉体抗水解性能的影响

doi:10.15541/jim20250063

无机材料学报 ›› 2025, Vol. 40 ›› Issue (7): 826-832.DOI: 10.15541/jim20250063

月桂酸改性剂对氮化铝粉体抗水解性能的影响

孙晶¹^,²(), 李翔¹(), 毛小建², 章健², 王士维²

1.上海理工大学材料与化学学院, 上海 200093
2.中国科学院上海硅酸盐研究所, 关键陶瓷材料全国重点实验室, 上海 200050

收稿日期:2025-02-17 修回日期:2025-04-02 出版日期:2025-07-20 网络出版日期:2025-04-09
通讯作者: 李翔, 教授. E-mail: xiangli@usst.edu.cn
作者简介:孙晶(2001-), 女, 硕士研究生. E-mail: sunjingwuhu@163.com
基金资助:
国家自然科学基金(U23A6014);国家自然科学基金(52272076);国家自然科学基金(52072245);国家自然科学基金(62471089);辽宁省科技计划联合计划项目(2024JH2/102600093)

Effect of Lauric Acid Modifier on the Hydrolysis Resistance of Aluminum Nitride Powders

SUN Jing¹^,²(), LI Xiang¹(), MAO Xiaojian², ZHANG Jian², WANG Shiwei²

1. School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China
2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 200050, China

Received:2025-02-17 Revised:2025-04-02 Published:2025-07-20 Online:2025-04-09
Contact: LI Xiang, professor. E-mail: xiangli@usst.edu.cn
About author:SUN Jing (2001-), female, Master candidate. E-mail: sunjingwuhu@163.com
Supported by:
National Natural Science Foundation of China(U23A6014);National Natural Science Foundation of China(52272076);National Natural Science Foundation of China(52072245);National Natural Science Foundation of China(62471089);Science and Technology Joint Plan Project of Liaoning Province(2024JH2/102600093)

摘要/Abstract

摘要：

氮化铝(AlN)陶瓷具有优异的热学和电学性能, 在电子封装和集成电路领域展现出极为广阔的应用前景。然而, AlN粉体易水解生成Al(OH)₃, 并在陶瓷烧结过程中热解生成Al₂O₃, 造成AlN陶瓷氧含量升高和热导率下降, 这严重制约了AlN陶瓷的制备和实际应用。因此, AlN粉体的表面改性对提升其抗水解性能至关重要。本研究使用聚乙二醇(Polyethylene Glycol, PEG)与月桂酸(Lauric Acid, LA)对AlN粉体进行表面改性以提升其抗水解性能, 通过简单的湿法球磨工艺, 使LA包覆在AlN粉体表面。FT-IR和XPS分析证实, LA羧基(-COOH)与AlN表面羟基氧化层发生类酯化反应, 形成化学键合的酯基。TEM表征结果显示, 酯化改性后的AlN粉体表面形成了厚度为12.2~16.1 nm的包覆层。将改性后的AlN粉体置于40 ℃水中72 h以上, 悬浮液pH维持在9以下, 物相结构和微观形貌均未发生变化。该包覆层化学性质稳定且具有低水溶性, 水分子难以扩散穿透包覆层引发水解反应。随着LA添加量增加, AlN粉体抗水解性能显著提升。本研究为提升AlN粉体抗水解性能及制备高性能AlN陶瓷提供了新途径。

关键词: 月桂酸, 氮化铝粉体, 抗水解, 表面改性

Abstract:

Aluminum nitride (AlN) ceramics exhibit exceptional thermal and electrical properties, making them highly promising candidates for electronic packaging applications and integrated circuits. Nevertheless, the hydrolysis of AlN powder results in formation of Al(OH)₃, which decomposes into Al₂O₃ during the subsequent sintering process. This reaction increases oxygen content, thereby degrading thermal conductivity of AlN ceramics and further imposing significant limitations on their processing and utilization. Consequently, surface modification of AlN powder is imperative to improve its hydrolysis resistance. In this work, a dual-agent modification strategy utilizing polyethylene glycol (PEG) and lauric acid (LA) was implemented through a straightforward wet ball-milling protocol, successfully forming a chemically bonded encapsulation layer on AlN particles. FT-IR and XPS analyses verified that carboxyl groups (-COOH) of LA engaged in esterification reactions with hydroxyl groups on the oxidized AlN surface, leading to formation of robust ester linkages. TEM images revealed a continuous encapsulation layer with a thickness ranging from 12.2 nm to 16.1 nm. Remarkably, the modified powder maintained a solution pH below 9 after 72 h immersion in water at 40 ℃, with no discernible alterations in phase composition and microscopic morphology. This chemically stable and low-solubility encapsulation layer effectively obstructs water diffusion pathways, thereby suppressing hydrolysis kinetics. Enhanced hydrolysis resistance was positively correlated with LA dosage. This work proposes an innovative encapsulation-based paradigm for developing hydrolysis-resistant AlN powders and advancing high-performance ceramic fabrication.

Key words: lauric acid, aluminum nitride powder, hydrolysis resistance, surface modification

中图分类号:

TQ174

孙晶, 李翔, 毛小建, 章健, 王士维. 月桂酸改性剂对氮化铝粉体抗水解性能的影响[J]. 无机材料学报, 2025, 40(7): 826-832.

SUN Jing, LI Xiang, MAO Xiaojian, ZHANG Jian, WANG Shiwei. Effect of Lauric Acid Modifier on the Hydrolysis Resistance of Aluminum Nitride Powders[J]. Journal of Inorganic Materials, 2025, 40(7): 826-832.

图/表 9

表1 AlN粉体水解实验条件

Table 1 Experimental conditions for hydrolysis of AlN powders

Sample	LA/% (in mass)	PEG/% (in mass)	Temperature/ ℃	Time/ h
AlN	-	-	-	-
AlN-72	-	-	40	72
0LA-2P-AlN	0	2	-	-
1LA-2P-AlN	1	2	-	-
3LA-2P-AlN	3	2	-	-
5LA-2P-AlN	5	2	-	-
7LA-2P-AlN	7	2	-	-
0LA-2P-AlN-72	0	2	40	72
1LA-2P-AlN-72	1	2	40	72
3LA-2P-AlN-72	3	2	40	72
5LA-2P-AlN-72	5	2	40	72
7LA-2P-AlN-72	7	2	40	72

图1 LA、AlN、AlN-72、7LA-2P-AlN和7LA-2P-AlN-72的FT-IR谱图

Fig. 1 FT-IR spectra of LA, AlN, AlN-72, 7LA-2P-AlN, and 7LA-2P-AlN-72

图2 AlN和7LA-2P-AlN的XPS全谱图

Fig. 2 XPS full spectra of AlN and 7LA-2P-AlN

表2 样品的XPS化学成分(原子分数)

Table 2 XPS chemical composition of the samples (in atom)

Sample	Al2p/%	N1s/%	C1s/%	O1s/%
AlN	36.26	13.12	11.24	39.38
7LA-2P-AlN	22.41	8.12	41.98	27.49

图3 AlN和7LA-2P-AlN的XPS谱图

Fig. 3 XPS spectra of AlN and 7LA-2P-AlN (a) Al2p; (b) N1s; (c) C1s; (d) O1s

图4 (a, b)初始AlN粉体和(c, d)7LA-2P-AlN粉体的TEM照片

Fig. 4 TEM images of (a, b) initial AlN powder and (c, d) 7LA-2P-AlN powder

图5 在40 ℃水中浸泡72 h改性前后AlN粉体悬浮液的pH

Fig. 5 pH of AlN powder suspensions before and after modification soaked in water at 40 ℃ for 72 h

图6 在40 ℃水中浸泡72 h改性前后AlN粉体的XRD图谱

Fig. 6 XRD patterns of AlN powders before and after modification soaked in water at 40 ℃ for 72 h

图7 AlN粉体水解前后的SEM照片

Fig. 7 SEM images of AlN powder before and after hydrolysis (a) AlN; (b) AlN-72; (c) 1LA-2P-AlN-72; (d) 3LA-2P-AlN-72; (e) 5LA-2P-AlN-72; (f) 7LA-2P-AlN-72

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月桂酸改性剂对氮化铝粉体抗水解性能的影响

Effect of Lauric Acid Modifier on the Hydrolysis Resistance of Aluminum Nitride Powders

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